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    Process for preparing trialkyl phosphites
    98.
    发明专利
    Process for preparing trialkyl phosphites 未知

    公开(公告)号：GB1028384A

    公开(公告)日：1966-05-04

    申请号：GB1238164

    申请日：1964-03-24

    Applicant: HOECHST AG

    Inventor： SCHERER OTTO ,  RAMMELT PETER PAUL

    IPC: C07F9/142

    Abstract: Trialkyl phosphites are obtained by reacting a saturated aliphatic monohydric alcohol containing 1 to 9 carbon atoms with a phosphorus trihalide in an amount of more than 2 moles per mol. of phosphorus trihalide in the presence of a diluent and an ammoniated water-soluble salt of an element of Group II of the Periodic Table in an amount sufficient to maintain a pH of at least 7 in the reaction mixture during and after the reaction at a temperature in the range from about -5 DEG C. to +10 DEG C. The process may be carried out by adding the ammoniated water-soluble salt to a mixture of the saturated aliphatic monohydric alcohol and a diluent in such an amount, that the proportion of ammonia contained in the said salt is at least 110% of the stoichiometric amount required for binding the hydrogen halide formed. The mixture obtained is then reacted with phosphorus trihalide. Alternatively, a smaller amount of the ammoniated water-soluble salt can be added to the mixture of the saturated aliphatic monohydric alcohol and the diluent, and during the reaction ammonia is introduced to reform the ammoniated salt. A further variant consists in adding a water-soluble salt, capable of being ammoniated, of an element of Group II of the Periodic Table to the mixture of the saturated aliphatic monohydric alcohol and the diluent, then introducing ammonia so that the salt is wholly or partially converted into the ammoniated compound, and then reacting with the phosphorus trihalide. When working in this manner ammonia is added until the pH of the reaction mixture is above 7. Suitable saturated aliphatic monohydric alcohols include primary and secondary alcohols such as methanol, ethanol, propanol-(1), propanol-(2), n-butanol-(1), n-butanol-(2), n-pentanol-(1), n-pentanol-(2), n-octanol-(1), 2-ethyl-hexanol-(1) either alone or in admixture with one another. Suitable phosphorus halides are phosphorus trichloride and tribromide. Larger quantities of alcohol may be used as a diluent. Suitable ammoniated compounds are the ammonia-addition compounds of water-soluble, dry or water-containing salts of Mg, Ca, Sr, Ba, Zn and/or Cd, capable of adding 1 to 8 mols. of ammonia. Suitable diluents include ethers, halogenated alkanes, aliphatic or cycloaliphatic hydrocarbons including phenyl cyclohexane. Examples are given for the preparation of trimethyl phosphite, triethyl phosphite and tributyl phosphite using phosphorus trichloride or phosphorus tribromide as the phosphorus halide in the presence of ammoniated calcium chloride; and of trimethyl phosphite using phosphorus trichloride in the presence of zinc tetramine chloride.

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